Liquid sample combustion apparatus



J. A. DE BLIEK LIQUID SAMPLE COMBUSTION APPARATUS Filed Jan. 4, 1965 9 M6 6 8 0 a 0 W 1%54fl 1 INVENTOR. John 4. 0e5/iek (i/ 1L & 46EN7' 5 1 11. 5 m F M 4 1 1 O40 W H HI I HH HI I I I l 1 |H Q Nov. 28, 1967 United States Patent 3,355,252 LIQUID SAMPLE COMBUSTION APPARATUS John A. De Bliek, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware Filed Jan. 4, 1965, Set. No. 422,957 8 Claims. (Cl. 23253) This invention relates to liquid organic sample combustion apparatus, and particularly to apparatus for achieving rapid quantitative decomposition of volatile organic liquids.

In the analysis of volatile organic liquids to determine total chlorine and sulphur present, in the range of .2 to 200 ppm, for example, it is desirable to have a simple, easy to use apparatus. Previously available apparatus has been satisfactory to use, but less convenient to use and more costly to purchase than has been desirable.

Accordingly, a principal object of this invention is to provide an improved liquid organic sample combustion unit for use in making chemical analyses.

Another object of this invention is to provide an improved burner for a liquid organic sample combustion unit.

A further object of this invention is to provide an improved sample introduction means for a liquid organic sample combustion unit.

In accordance with this invention there is provided an organic sample combustion unit comprising a sample injection device which is an enclosed vessel having a gas and sample inlet tube which extends to near the bottom of the vessel and a gas and vaporized sample outlet tube which extends from the upper end of the enclosed vessel. The sample injection device is at least partially immersed in a bath which is at a temperature such that the sample has substantial vapor pressure. The gas and vaporized sample tube is coupled to a sample burner assembly which includes, within an enclosed glass walled housing an elongated gas and sample tube having an orifice at one end, a tubular sleeve of larger diameter than said tube telescoped partially over said end, but extending above the end, an oxygen feed tube for dispensing oxygen in the direction of said sleeve and above the end of the sleeve which extends beyond said gas and sample tube, and tubular means for withdrawing from said housing the products of combustion of said sample, gas and oxygen.

The combustion products are then condensed and collected for use in an analytical procedure.

The gas with which the sample is volatilized is hydrogen. The burning, because of the presence of the sleeve, takes place above the orificed end of the gas and sample tube, without carbonizing.

The invention, as well as additional objects and advantages thereof, will best be understood when the following detailed description is read in connection with the accompanying drawing, in which:

FIG. 1 is a side elevational view, partly broken away and in section, of apparatus in accordance with this invention, and

FIG. 2 is an isometric view of a burner assembly in accordance with this invention.

Referring to the drawing, there is shown liquid sample combustion apparatus, indicated generally by the numeral 10, which comprises, within a supporting framework or housing 11, an enclosed sample and gas receiving vessel 12 having inwardly extending protuberances 50 on its side walls, a gas and sample inlet tube 14 having a gas (hydrogen) line 16 coupled thereto and having its lower end 20 disposed near the bottom of the vessel 12. Sample is introduced to the tube 14 through a suitable septum 15,

for example, a gas and vaporized sample outlet tube 22 extends from the upper part of the vessel 12.

The vessel 12 is disposed within a beaker (for example) 44 which contains an oil heat transferring agent 46. The beaker is heated by means of an electrical heater 18 to which electrical power is supplied by leads 36, 38 which are coupled to conventional control means (not shown) in the compartment 34.

The burner assembly 24, shown in detail in FIG. 2, comprises a base assembly 54 which is actually a glass stopper through which the gas and vaporized sample tube 22, anoxygen inlet tube 26, and a combustion products tube 28 extend and are sealed.

The gas and vaporized sample tube 22 extends above the rim 23 of the stopper 54 and, as previously mentioned, has an orifice 58 in its end. A sleeve 62, of sub stantially larger diameter than the diameter of the tube 22, fits over the orificed end of the tube 22 and rests on the rim 23 of the tapered section 60 of the stopper 54. The sleeve 62 has an outwardly flared part 63 which is disposed above the orifice 58.

The oxygen tube 26 extends above the sleeve 62 and has an outlet orifice 64 which is directed toward and above the flared end 63 of the sleeve 62. The orifice 64 is disposed closer to the longitudinal axis of the gas and vaporized sample outlet tube than is the rim of the fiared part 63 of the sleeve 62.

The oxygen tube 28 has a small bore 52 inside the stopper 54.

The combustion products tube 28 extends substantially above the orifice 64 and has an Open end 66.

A bulb 56 fits over the tubes 22, 26, 28 and is fitted at its lower end to the tapered part 60 of the stopper 54.

The part of the combustion products tube 28 which extends below the burner assembly is coupled to a condenser 30 having coolant inlet means 40 and coolant outlet means 42 coupled thereto.

The combustion products are collected in a container 32.

The compartment 34 contains (though not shown) hydrogen and oxygen flow control means and, as previously mentioned, electrical power control means.

Mechanical means for supporting the above described apparatus within the housing or framework 11 has, for the sake of simplicity in the drawing, not been shown.

In operation, sample liquid 48 is injected through the septum 15 into the vessel 21. Hydrogen gas, entering the vessel through the orificed end 20 of the tube 14, bubbles upwardly through the sample liquid which is heated by means of the heater 18 and liquid 46 in the beaker 44 so that it has a substantial vapor pressure. The vaporized sample is carried in the hydrogen gas stream into the burner assembly through the tube 22, escaping through the orifice 58.

Oxygen from the tube 26 is directed through the orifice 64 above the sleeve 63 and towards the gas and vaporized sample.

Burning of the sample takes place at or near the upper flared end of the sleeve 63, away from the orifice 58 and upper end of the tube 22.

Combustion is substantially complete, with substantially no carbon or incomplete combustion product collecting in the burner assembly. Though the sleeve 62 is of large diameter and is, relatively speaking, well cooled, it does occasionally have to be replaced as it becomes deteriorated.

When no sleeve is used, however, the oxygen and vaporized sample and hydrogen do not have sufiicient opportunity to completely mix before they are burned, leaving incompletely burned sample on the upper end part of the tube 22. In addition, the upper end part, under such conditions, becomes excessively heated and deteriorates. This results in changes in orifice size and eventually in the substantial inoperativeness of the burner assembly.

Oxygen escaping into the burner assembly 24 through the orifice 52 gently sweeps completely burned sample and hydrogen upwardly through the combustion zone and thence out of the assembly through the tube 28.

The apparatus of this invention is easy to manufacture and use, is simple and reliable to operate, and is comparatively speaking, economical to manufacture.

The burner assembly tubes and vessel 12 are made of glass or other material which does not react with the sample or fuel.

The sleeve 62, being substantially larger in diameter than the diameter of the tube 22, slides easily over the end of the tube 22.

What is claimed is:

1. Liquid sample combustion apparatus comprising (A) an enclosed sample injection vessel having a top,

bottom, and side walls, a fuel .gas and sample inlet tube ending adjacent to said bottom, means for coupling gas to said gas and sample inlet tube, means for inserting sample liquid into said gas and sample inlet tube, a gas and sample outlet tube, said outlet tube being coupled to the top part of said vessel;

(B) means for heating said sample injection vessel;

(C) a sample burner assembly having, within an enclosed elongated envelope, a top and bottom, a vaporized sample and fuel gas tubular element having an orifice at one end thereof, a sleeve, said sleeve surrounding the orificed end of said sample and fuel gas tubular element and extending beyond said end, said sleeve having a diameter substantially larger than the diameter of said sample and fuel gas tubular element, an oxygen inlet tube, said oxygen inlet tube having an orifice directed towards the longitudinal axis of said sleeve and slightly above the end of the sleeve which extends beyond said sample and fuel gas tubular element, means near the top of said envelope for withdrawing combustion products from said envelope, and

(D) means for condensing combustion products removed from said burner assembly.

2. Apparatus in accordance with claim 1, wherein said sleeve has an outwardly flared part which extends beyond said orificed end of said sample and fuel gas tubular element.

3. Apparatus in accordance with claim 1, wherein said sleeve is removably mounted in said envelope.

4. Apparatus in accordance with claim 1, wherein said oxygen inlet tube has a curved end which contains said orifice.

5. Apparatus in accordance with claim 1, wherein said oxygen inlet tube has a small bore adjacent to the bottom of said envelope.

6. Apparatus in accordance with claim 1, wherein said means for withdrawing combustion products is a tube which passes through the bottom of said envelope and extends to near the top of said envelope.

7. Apparatus in accordance with claim 1, wherein said sample injection vessel has inwardly extending protuberances on its side walls.

8. A liquid sample burner assembly for use in analyzing small samples of organic liquids comprising, within an enclosed elongated envelope, having a top and bottom, a vaporized sample and fuel gas tubular element having an orifice at one end thereof, a sleeve, said sleeve surrounding the orificed end of said sample and fuel gas tubular element and extending away from said orificed end for a short distance in either direction longitudinally thereof, said sleeve having a diameter substantially larger than the diameter of said sample and fuel gas tubular element and being open at its ends, an oxygen inlet tube, said oxygen inlet tube having an orifice directed towards the longitudinal axis of said sleeve and slightly above the end of the sleeve which extends beyond said sample and fuel gas tubular element, and means near the top of said envelope for withdrawing combustion products from said envelope.

References Cited UNITED STATES PATENTS 716,049 12/1902 Jenkins 15873 2,556,196 6/1951 Krejci 23259.5 X

JAMES H. TAYMAN, 111., Primary Examiner. 

1. LIQUID SAMPLE COMBUSTION APPARATUS COMPRISING (A) AN ENCLOSED SAMPLE INJECTION VESSEL HAVING A TOP, BOTTOM, AND SIDE WALLS, A FUEL GAS AND SAMPLE INLET TUBE ENDING ADJACENT TO SAID BOTTOM, MEANS FOR COUPLING GAS TO SAID GAS AND SAMPLE INLET TUBE, MEANS FOR INSERTING SAMPLE LIQUID INTO SAID GAS AND SAMPLE INLET TUBE, A GAS AND SAMPLE OUTLET TUBE, SAID OUTLET TUBE BEING COUPLED TO THE TOP PART OF SAID VESSEL; (B) MEANS FOR HEATING SAID SAMPLE INJECTION VESSEL; (C) A SAMPLE BURNER ASSEMBLY HAVING, WITHIN AN ENCLOSED ELONGATED ENVELOPE, A TOP AND BOTTOM, A VAPORIZED SAMPLE AND FUEL GAS TUBULAR ELEMENT HAVING AN ORIFICE AT ONE END THEREOF, A SLEEVE, SAID SLEEVE SURROUNDING THE ORIFICED END OF SAID SAMPLE AND FUEL GAS TUBULAR ELEMENT AND EXTENDING BEYOND SAID END, AID SLEEVE HAVING A DIAMETER SUBSTANTIALLY LARGER THAN THE DIAMETER OF SAID SAMPLE AND FUEL GAS TUBULAR ELEMENT, AN OXYGEN INLET TUBE, SAID OXYGEN INLET TUBE HAVING AN ORIFICE DIRECTED TOWARDS THE LONGITUDINAL AXIS OF SAID SLEEVE AND SLIGHTLY ABOVE THE END OF THE SLEEVE WHICH EXTENDS BEYOND SAID SAMPLE AND FUEL GAS TUBULAR ELEMENT, MEANS NEAR THE TOP OF SAID ENVELOPE FOR WITHDRAWING COMBUSTION PRODUCTS FROM SAID ENVELOPE, AND (D) MEANS FOR CONDENSING COMBUSTION PRODUCTS REMOVED FROM SAID BURNER ASSEMBLY. 